1. Technical Field of the Invention
The present invention relates to methods and materials for the removal of pollutants from flue gas or product gas from a gasification system. In particular, mercury is removed from gas streams generated during the burning or gasification of fossil fuels by highly reactive regenerable sorbents.
2. Background of the Invention
The combustion and gasification of fossil fuel such as coal generates flue gas that contains mercury and other trace elements that originate from the fuel. The release of the mercury (and other pollutants) to the environment must be controlled by use of sorbents, scrubbers, filters, precipitators, and other removal technologies. Mercury is initially present in the elemental form during combustion and gasification. In downstream process sections, such as in the ducts and stack of a combustion system, some of the elemental mercury is oxidized. The amount that is oxidized depends on the amount of acid gases present in the flue gas and other factors. Amounts of mercury vary with the fuel, but concentrations of mercury in the stream of flue gas from coal combustion are typically less than 5 parts per billion (ppb). Large coal combustion facilities such as electric utilities may emit a pound of mercury, or more, a day. Mercury removal applications include, without limitation, flue gas from coal (or other fossil fuel) combustion, waste incineration, product gas from gasification, as well as offgases from mineral processing, metal refining, retorting, cement manufacturing, chloralkali plants, dental facilities, and crematories.
Mercury Sorbent Technologies
Several types of mercury control methods for flue gas have been investigated, including injection of fine sorbent particles into a flue gas duct and passing the flue gas through a sorbent bed. Fine-particle injection sorbents include activated carbon, metal oxide sorbent, sodium sulfide particles, and basic silicate or oxide sorbents. When particle injection is employed, the mercury captured on the sorbent particles is removed from the gas stream in a particulate control device such as a baghouse or electrostatic precipitator (ESP) and collected along with ash particulate. The sulfide and basic silicate and oxide particles are effective only for the oxidized mercury, and the metal oxide sorbents exhibit slower capture kinetics than the carbon particles. Additionally, injection of fine carbon particles into the flue gas stream has been only partially successful in removing mercury, especially elemental mercury, where effective removal of only about 60% is attained for some applications with a FF (fabric filter) to collect carbon and ash. Even lower removal rates have been observed when an ESP is used to collect the carbon because the contact time of the carbon with the gas is very short.
A major problem with existing carbon injection systems is that the sorbent is relatively unreactive toward mercury. Consequently, these sorbents must be used in large amounts, at high sorbent-to-mercury ratios, to effectively capture the mercury. These sorbents tend to be relatively expensive and cannot be easily separated from the ash for regeneration and reuse. The collection of carbon in the ash also creates solid waste disposal problems, and the spent sorbent may contaminate the collected ash, preventing its use in various applications.
One solution has been to add an oxidative sorbent comprising an aluminosilicate material impregnated with a very heavy dosage of one or more oxidative metal halides plus activated carbon. For example, refer to Varma et al. (20070140940). However, the amounts of metal salts required for Hg oxidation are generally relatively large and expensive. Also, several of the salts that can be used in such a process are highly toxic. Although the metal salts are present for oxidation in this process, activated carbon is essential for getting adsorption of the Hg. As such, there is no synergistic role for the aluminosilicates as they appear to be only a support for the oxidizing salts.
Another approach has been the injection of aluminosilicate particulate such as bentonite, which contains neither oxidizing salts nor halogen complexes with a Lewis base site, and thus lacks the more powerful oxidizing capability of the said complexes as described in this application. For example, see U.S. Pat. No. 7,413,719. Additionally, the injection of an aluminosilicate (kaolin or metakaolin) containing calcium hypochlorite which thermally decomposes to form halogen is also known. For example, see U.S. Patent Application No. 20030103882. Thus these and similar impregnated aluminosilicate technologies require time in flight at appropriate high temperatures to heat the impregnated salt(s) to generate an oxidation site. This clearly represents a kinetic barrier to activation in contrast to the extremely fast complexing reaction of the Lewis acid on the surface of the appropriate Lewis base sorbent described in the present patent. The kinetic barrier is only for heating up the calcium hypochlorite to decompose it to Cl atoms or molecules. Halogen (bimolecular or atomic) would complex with carbon or noncarbon at any lower temperature to form reactive oxidation sites. Also, halide would require a very high temp or strong acid to form reactive halogen or halogen complex.
Yet another approach is the injection of bentonite plus a metal sulfide and a metal salt, none of which is oxidizing to elemental mercury and would require a slow thermal activation step. For example, see U.S. Patent Application No. 20070119300.
The injection of halogen or halogen precursors in a hot zone, followed by contact with an alkaline material in a wet or dry scrubber is another approach known in the art. With such an approach, elemental mercury is claimed to be oxidized by the halogen to Hg(II) which is collected by the alkaline material in the scrubber. For example, see U.S. Pat. No. 6,808,692 (Oehr), U.S. Pat. No. 3,849,267 (Hilgen), U.S. Pat. No. 5,435,980 (Felsvang), U.S. Pat. No. 6,375,909 (Dangtran), U.S. Patent Application No. 20020114749 (Cole), U.S. Pat. No. 6,638,485 (Iida), U.S. Patent Application No. 20030185718 (Sellakumar), U.S. Patent Application No. 20030147793 (Breen), and U.S. Pat. No. 6,878,358 (Vosteen). However, even though it is known to inject halogen forms at some stage of the combustion process, such a process does not utilize a complexing method on a sorbent surface for conducting the oxidation and capture. Further, the alkaline material is rapidly surface-coated by the large concentrations of acid gases, lowering its capacity for adsorption of Hg(II). It is also recognized that the halogen forms initially introduced or generated are far more reactive to the large concentrations of SO2 and moisture in the flue gas, and so gas-phase reactions of the halogens with Hg are hindered. In contrast, the present invention takes advantage of the Lewis acid complexes that rapidly form on the sorbent surface to effect the Hg oxidation, rather than rely on gas phase reactions for oxidation. Thus HCl, HBr, SO2Br, and other gas-phase products all festoon the surface and promote the activity of the sorbent by forming complexes with the sorbent to form a promoted sorbent.
Accordingly, there remains a need for more economical and effective mercury removal technology. This invention provides for cost-effective removal of pollutants, including mercury, using sorbent enhancement additives and/or highly reactive sorbents, with contact times of seconds (or less), and that may be regenerated and reused.